CN101563383B - Fluorochemical urethane compounds having pendent silyl groups - Google Patents

Abstract

Fluorochemical urethane compounds and coating compositions derived therefrom are described. The compounds and compositions may be used in treating substrates, in particular substrates having a hard surface such as ceramics or glass, to render them water, oil, stain, and soil repellent.

Description

Fluorochemical urethane compound having side chain silyl group

Technical Field

The present invention relates to fluorochemical urethane compounds and coating compositions derived therefrom that are useful for treating substrates, particularly substrates having a hard surface such as ceramic or glass, to render them water, oil, stain, and soil repellent.

Background

While many fluorinated compositions are known in the art for treating substrates to render them oil and water repellent, there is a continuing need to further provide substrates with improved compositions for substrate treatment, particularly substrates having hard surfaces such as ceramics or glass and stone, in order to render them water repellent, oil repellent, and easy to clean. There is also a need to treat glass and plastics, particularly in the optical field, as hard surfaces in order to make them resistant to stains, dirt and dust. Advantageously, such compositions and methods of using them can produce coatings with improved properties. In particular, it is desirable to improve the durability of the coating, including improving the wear resistance of the coating. Furthermore, improving the ease of cleaning of such substrates while using less detergent, water or physical labor is not only desired by the end consumer, but also has a positive impact on the environment. In addition, it is desirable that the coatings exhibit particularly good chemical and solvent resistance. The composition should be conveniently used in an easy and safe manner and be compatible with existing manufacturing methods. Preferably, the composition is readily adaptable to practice manufacturing methods for producing the substrate to be treated.

Disclosure of Invention

The present invention provides fluorochemical urethane compounds of the formula:

wherein R is_fIs a fluorine-containing group including a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group and/or a perfluorooxyalkylene group,

R¹is the residue of a polyisocyanate, has a valence of x + y,

R²is a silane-containing moiety derived from the michael reaction between an acryloyl group and an aminosilane,

x and y are each independently at least 1 and z is 1 or 2.

In one aspect, the present invention relates to chemical compositions comprising one or more compounds (where z is 1) or oligomers (where z is 2) and mixtures thereof having at least one fluorine-containing group and at least one silane-containing moiety derived from a Michael reaction between a nucleophilic acryloyl compound (e.g., an acrylated polyol having at least one isocyanate-reactive hydroxyl group) and an aminosilane.

As used herein, the term "oligomer" refers to a polymer molecule consisting of only a few, i.e. at most an average of 10, but preferably at most an average of 5, repeating (polymerized) or repeatable units. Each repeating unit includes a polyisocyanate residue derived from the reaction of at least one nucleophilic fluorine-containing compound, an aminosilane, a polyisocyanate, wherein the fluorine-containing moiety is selected from the group consisting of perfluoroalkyl, perfluoroalkylene, perfluorooxyalkyl, and perfluorooxyalkylene. The oligomer may be end-capped with one or more perfluoroalkyl groups, one or more perfluorooxyalkyl groups, and/or one or more silyl groups.

These compounds or oligomers may include the michael reaction product of an aminosilane with a fluorochemical urethane compound having a pendant acryloyl group; the urethane compound comprises the reaction product of a polyisocyanate, a nucleophilic fluorine-containing compound having one or two nucleophilic isocyanate-reactive functional groups, and a nucleophilic acryloyl compound. In another embodiment, the compound may include the Michael reaction product of an aminosilane with a nucleophilic acryloyl compound, and the subsequent reaction product with a polyisocyanate and a fluorine-containing nucleophilic compound.

Unless otherwise defined, the following terms used in the specification and claims have the meanings given below:

"alkyl" means a straight or branched, cyclic or acyclic, saturated monovalent hydrocarbon group having from 1 to about 12 carbon atoms, such as methyl, ethyl, 1-propyl, 2-propyl, pentyl, and the like.

"acryloyl" refers to acrylate, thioacrylate, or acrylamide.

"alkylene" means a straight chain saturated divalent hydrocarbon radical having from 1 to about 12 carbon atoms or a branched saturated divalent hydrocarbon radical having from 3 to about 12 carbon atoms, such as methylene, ethylene, propylene, 2-methylpropylene, pentylene, hexylene, and the like.

"alkoxy" refers to an alkyl group having a terminal oxygen atom, e.g., CH₃-O-、C₂H₅-O-, and the like.

"aralkylene" refers to an alkylene group as defined above having an aryl group attached to the alkylene group, e.g., benzyl, 1-naphthylethyl, and the like.

"cured chemical composition" means drying the chemical composition, or evaporating solvent from the chemical composition from ambient temperature or higher until dry. The composition may be further crosslinked, resulting in formation of siloxy bonds between the urethane compounds.

"nucleophilic fluorine-containing compound" refers to compounds having one or two nucleophilic, isocyanate-reactive functional groups, such as hydroxyl or amine groups, and perfluoroalkyl, perfluoroalkylene, perfluorooxyalkyl, or perfluorooxyalkylene groups, such as CF₉SO₂N(CH₃)CH₂CH₂OH，C₄F₉CH₂CH₂OH，C₂F₅O(C₂F₄O)₃CF₂CONHC₂H₄OH，c-C₆F₁₁CH₂OH and the like.

"fluorochemical urethane compounds" refer to compounds of formula I and include those having urethane linkages per se or alternatively urea and/or thiourea linkages.

By "hard substrate" is meant any rigid material that maintains its shape, such as glass, ceramic, concrete, natural stone, wood, metal, plastic, and the like.

"Oxoalkoxy" has essentially the meaning given above for alkoxy, except that one or more oxygen atoms may be present in the alkyl chain and the total number of carbon atoms present may be up to 50, for example CH₃CH₂OCH₂CH₂O-，C₄H₉OCH₂CH₂OCH₂CH₂O-，CH₃O(CH₂CH₂O)_1-100H, and the like.

"Oxyalkyl" has essentially the meaning given above for alkyl, except that one or more oxygen heteroatoms may be present in the alkyl chain, which heteroatoms are separated from each other by at least one carbon atom, e.g. CH₃CH₂OCH₂CH₂-，CH₃CH₂OCH₂CH₂OCH(CH₃)CH₂-，C₄F₉CH₂OCH₂CH₂-, and the like.

"oxyalkylene" has essentially the meaning given above for alkylene, except that one or more oxygen heteroatoms may be present in the alkylene chain, which heteroatoms are separated from each other by at least one carbon atom, e.g. -CH₂OCH₂O-，-CH₂CH₂OCH₂CH₂-，-CH₂CH₂OCH₂CH₂CH₂-, and the like.

"halo" means fluoro, chloro, bromo or iodo, preferably fluoro and chloro.

"perfluoroalkyl" has essentially the meaning given above for "alkyl" except that all or substantially all of the hydrogen atoms of the alkyl group have been replaced with fluorine atoms and the number of carbon atoms is from 1 to about 12, e.g., perfluoropropyl, perfluorobutyl, perfluorooctyl, and the like.

"perfluoroalkylene" has essentially the meaning given above for "alkylene" except that all or substantially all of the hydrogen atoms of the alkylene are replaced with fluorine atoms, e.g., perfluoropropylene, perfluorobutylene, perfluorooctylene, and the like.

"Perfluorooxyalkyl" has essentially the meaning given above for "oxyalkyl", with all or essentially all of the hydrogen atoms of the oxyalkyl being replaced by fluorine atoms and the number of carbon atoms being other than from 3 to about 100, e.g. CF₃CF₂OCF₂CF₂-，CF₃CF₂O(CF₂CF₂O)₃CF₂CF₂-，C₃F₇O(CF(CF₃)CF₂O)_sCF(CF₃)CF₂-, (where s is, for example, from about 1 to about 50), and the like.

"Perfluoroalkyloxyalkylene" has essentially the meaning given above for "oxyalkylene" with all or essentially all of the hydrogen atoms of the oxyalkylene groups being replaced by fluorine atoms and with the exception of carbon atoms in the range of from 3 to about 100, e.g., -CF₂OCF₂-, or- [ CF₂-CF₂-O]_r-[CF(CF₃)-CF₂-O]_s-; where r and s are, for example, integers from 1 to 50.

"perfluorinated groups" refers to organic groups in which all or substantially all of the carbon-bonded hydrogen atoms are replaced with fluorine atoms, such as perfluoroalkyl groups, perfluorooxyalkyl groups, and the like.

"polyfunctional isocyanate compound" or "polyisocyanate" means a compound containing an average of greater than 1, preferably 2 or more, isocyanate-NCO groups attached to a polyvalent organic group, such as hexamethylene diisocyanate, the biuret and isocyanurate of hexamethylene diisocyanate, and the like.

"nucleophilic acryloyl compound" refers to an organic compound having at least one primary or secondary nucleophilic isocyanate-reactive group and at least one acryloyl group per molecule, including acrylate and acrylamide groups.

"Michael addition" refers to an addition reaction in which an aminosilane is subjected to addition of acryloyl groups 1, 4.

Detailed Description

The present invention provides fluorochemical urethane compounds of the formula described below.

Wherein

R_fIs a fluorine-containing group including a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group and/or a perfluorooxyalkylene group,

R¹is the residue of a polyisocyanate, has a valence of x + y,

R²is a silane-containing moiety derived from the michael reaction between an acryloyl group and an aminosilane,

x and y are each independently at least 1 and z is 1 or 2.

For formula I, R²From the Michael addition of an aminosilane to an acryloyl group, as shown in the following formula:

wherein

X¹is-O-or-S-,

X²is-O, -S-or-NR⁴-, wherein R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

R³is a polyvalent alkylene or arylene group, or combinations thereof, said alkylene group optionally containing one or more catenary oxygen atoms;

R⁵is C₁-C₄Alkyl, or-R⁶-Si(Y_p)(R⁷)_3-p；

R⁶Is a divalent alkylene group, optionally containing one or more catenary oxygen atoms;

y is a hydrolyzable group, and Y is a hydrolyzable group,

R⁷is a monovalent alkyl or aryl radical, and is,

p is 1, 2 or 3, preferably 3, and

q is 1 to 5, preferably 2 to 5.

While the inventors do not wish to be bound by theory, it is believed that the compound of formula I above undergoes a condensation reaction with the substrate surface to form a siloxane layer by hydrolysis or displacement of the hydrolysable "Y" group of formula II. In this context, "siloxane" means a-Si-O-Si-bond to the compound of formula I. In the presence of water, the "Y" group will hydrolyze the "Si-OH" group, further condensing to siloxane.

Coatings prepared from coating compositions comprising compounds of formula I include the compounds themselves, as well as siloxane derivatives resulting from bonding to the surface of a predetermined substrate and through intermolecular crosslinking of the siloxane form. The coating may also include unreacted or uncondensed "Si-Y" groups. The composition may further include non-silane species such as oligomeric perfluorooxyalkyl monohydrides, starting materials, perfluorooxyalkyl alcohols and esters.

In one embodiment, the present invention provides a coating composition comprising a compound of formula I, a solvent, and optionally water and an acid. In another embodiment, the coating composition comprises an aqueous suspension or dispersion of the compound. In order to obtain good durability of many substrates, such as ceramics, the composition of the present invention preferably comprises water. Accordingly, the present invention provides a coating process comprising the step of providing a substrate in contact with a coating composition comprising a compound of formula I and a solvent. The coating composition may further comprise water and an acid. In one embodiment, the method comprises contacting the substrate with a coating composition comprising a silane of formula I and a solvent, followed by contacting the substrate with an aqueous acid.

Polyisocyanates useful in preparing the fluorochemical compounds of the present invention include a linkage to a polyvalent organic group (R)¹) The polyvalent organic group may comprise a polyvalent aliphatic, alicyclic or aromatic moiety; or a polyvalent aliphatic, alicyclic or aromatic moiety attached to a biuret, isocyanurate, or uretdione, or mixtures thereof. Preferred polyfunctional isocyanate compounds contain an average of at least two isocyanate (-NCO) groups. The compounds comprising at least two-NCO groups are preferably composed of divalent or trivalent aliphatic, cycloaliphatic, araliphatic or aromatic groups which are linked to the-NCO groups. Aliphatic divalent or trivalent groups are preferred.

Representative examples of suitable polyisocyanate compounds include isocyanate functional derivatives of isocyanate compounds as defined herein. Examples of derivatives include (but are not limited to) those selected from the group consisting of: ureas, biurets, allophanates, dimers and trimers of isocyanates (e.g., uretdiones and isocyanurates), and mixtures thereof. Any suitable organic polyisocyanate such as aliphatic, alicyclic, araliphatic or aromatic polyisocyanate may be used alone or in a mixture of two or more.

Aliphatic polyisocyanate compounds generally provide better light stability than aromatic compounds. On the other hand, aromatic polyisocyanate compounds are generally more economical and more reactive towards nucleophiles than aliphatic polyisocyanate compounds. Suitable aromatic isocyanurate compounds include, but are not limited to, those selected from the group consisting of: 2, 4-Toluene Diisocyanate (TDI), 2, 6-toluene diisocyanate, TDI adduct with trimethylolpropane (under the trade name Desmodur)^TMCB from Bayer of Pittsburgh, Pa.), isocyanurate trimer of TDI (under the name Desmodur)^TMIL is from Bayer corporation of Pittsburgh, Pa.), diphenylmethane-4, 4' -diisocyanate (MDI), diphenylmethane-2,4' -diisocyanate, 1, 5-diisocyanato-naphthalene, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, 1-methoxy-2, 4-phenylene diisocyanate, 1-chlorophenyl-2, 4-diisocyanate, and mixtures thereof.

Examples of useful cycloaliphatic hydrocarbon polyisocyanate compounds include, but are not limited to, those selected from the group consisting of: dicyclohexylmethane diisocyanate (H)₁₂MDI under the trade name Desmodur^TMCommercially available from bayer corporation of pittsburgh, pennsylvania), 4' -isopropyl-bis (cyclohexyl isocyanate), isophorone diisocyanate (IPDI), cyclobutane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate (CHDI), 1, 4-cyclohexane bis (methylene isocyanate) (BDI), dimer acid diisocyanate (from bayer corporation), 1, 3-bis (diisocyanatomethyl) cyclohexane (H)₆XDI), 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate, and mixtures thereof.

Examples of useful aliphatic polyisocyanate compounds include, but are not limited to, those selected from the group consisting of: tetramethylene-1, 4-diisocyanate, hexamethylene-1, 6-diisocyanate (HDI), octamethylene-1, 8-diisocyanate, 1, 12-diisocyanatododecane, 2, 4-trimethyl-hexamethylene diisocyanate (TMDI), 2-methyl-1, 5-pentamethylene diisocyanate, dimer diisocyanate, urea of hexamethylene diisocyanate, biuret (HDI) of hexamethylene-1, 6-diisocyanate (trade name Desmodur)^TMN-100 and N-3200 from Bayer corporation of Pittsburgh, Pa.), isocyanurate of HDI (available under the trade name Desmodur^TMN-3300 and Desmodur^TMN-3600 available from Bayer corporation of Pittsburgh, Pa.), a blend of isocyanurate of HDI and uretdione of HDI (under the trade name Desmodure)^TMN-3400 available from bayer corporation of pittsburgh, pa), and mixtures thereof.

Examples of useful araliphatic polyisocyanates include, but are not limited to, those of the group consisting of: m-tetramethylxylylene diisocyanate (m-TMXDI), p-tetramethylxylylene diisocyanate (p-TMXDI), 1, 4-Xylylene Diisocyanate (XDI), 1, 3-xylylene diisocyanate, p- (1-isocyanatoethyl) phenyl isocyanate, m- (3-isocyanatobutyl) phenyl isocyanate, 4- (2-isocyanatocyclohexyl-methyl) phenyl isocyanate, and mixtures thereof.

Preferred polyisocyanates generally include those selected from the group consisting of: tetramethylene-1, 4-diisocyanate, hexamethylene-1, 6-diisocyanate (HDI), octamethylene-1, 8-diisocyanate, 1, 12-diisocyanatododecane, and the like, and mixtures thereof. The fluorochemical compositions of the present invention comprise compounds or oligomers made using the preferred polyisocyanates that impart higher receding dynamic contact angles of water and hexadecane. Higher water receding dynamic contact angles and higher hexadecane receding dynamic contact angles are generally indicative of good water and oil repellency properties.

Fluorochemical urethanes include, in part, fluorochemical compounds having a mono-or difunctional perfluorinated group and at least one nucleophilic isocyanate-reactive functional group. Such compounds include those represented by the following formula:

R_f ¹-[Q(X²H)_y]_z，(III)

wherein

R_f ¹Is a monovalent perfluoroalkyl or perfluorooxyalkyl group (wherein z is 1), or a divalent perfluoroalkylene or perfluorooxyalkylene group (wherein z is 2),

q is a covalent bond, or a z-valent polyvalent alkylene group optionally containing one or more catenary (in-chain) nitrogen or oxygen atoms, and optionally containing one or more sulfonamide, carboxamide, or carboxyl functional groups;

X²is-O-, -NR-⁴-or-S-, wherein R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

y is 1 or 2, and

z is 1 or 2.

For formulas I and III, the reaction between the nucleophilic fluorine-containing compound (III) and the isocyanate groups of the polyisocyanate produces a urea-or urethane-linked fluorine-containing group. Thus R of formula I_fRepresented by formula IV.

Wherein

R_f ¹Is a monovalent perfluoroalkyl or perfluorooxyalkyl group (wherein z is 1), or a divalent perfluoroalkylene or perfluorooxyalkylene group (wherein z is 2),

q is a covalent bond, or a z-valent polyvalent alkylene group optionally containing one or more catenary (in-chain) nitrogen or oxygen atoms, and optionally containing one or more sulfonamide, carboxamide, or carboxyl functional groups;

X²is-O-, -NR⁴-or-S-, wherein R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

y is 1 or 2, and

z is 1 or 2.

R of formulae III and IV_f ¹The groups may comprise linear, branched, or cyclic fluorochemical groups or any combination thereof. R_f ¹The group may be monovalent or divalent, and optionally contains one or more catenated oxygen atoms in the carbon-carbon chain so as to form a carbon-oxygen-carbon chain (i.e., perfluorinatedOxyalkylene groups). Fully fluorinated groups are generally preferred, but hydrogen or other halogen atoms may also be present as substituents, provided that no more than one of every two carbon atoms is present.

Preference is furthermore given to any R_f ¹The group contains at least about 40% by weight fluorine, more preferably at least about 50% by weight fluorine. Monovalent R_f ¹The terminal part of the group is generally fully fluorinated, preferably containing at least 3 fluorine atoms, e.g. CF₃-、CF₃CF₂-、CF₃CF₂CF₂-、(CF₃)₂N-、(CF₃)₂CF-、SF₅CF₂-. In certain embodiments, a monovalent perfluoroalkyl group (i.e., formula C)_nF_2n+1Of (a) or a divalent perfluoroalkylene group (i.e. of formula-C)_nF_2n-those wherein n is 2 to 12 (including 2 and 12) is preferably R_f ¹More preferably, n-3 to 5, and most preferably n-4.

Useful perfluorooxyalkyl and perfluorooxyalkylene radicals R_f ¹The radicals correspond to the formula:

W-R_f ³-O-R_f ⁴-(R_f ⁵)_q-(V)

wherein

W is fluorine of a monovalent perfluorooxyalkyl group and is the opening ("-") of a divalent perfluorooxyalkylene group;

R_f ³represents a perfluoroalkylene group, R_f ⁴Denotes a perfluoroalkyleneoxy group consisting of perfluoroalkyleneoxy groups having 1, 2, 3, or 4 carbon atoms or mixtures of such perfluoroalkyleneoxy groups, R_f ⁵Represents a perfluoroalkylene group and q is 0 or 1. Perfluoroalkylene R in formula (IV)_f ³And R_f ⁵May be straight or branched chain and may comprise from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms. A typical monovalent perfluoroalkyl group is CF₃-CF₂-CF₂-, a typical divalent perfluoroalkylene group is-CF₂-CF₂-CF₂-、-CF₂-or-CF (CF)₃)CF₂-. Perfluoroalkyleneoxy radical R_f ⁴Examples of (a) include: -CF₂-CF₂-O-、-CF(CF₃)-CF₂-O-、-CF₂-CF(CF₃)-O-、-CF₂-CF₂-CF₂-O-、-CF₂-O-、-CF(CF₃) -O-, and-CF₂-CF₂-CF₂-CF₂-O。

Perfluoroalkyleneoxy radical R_f ⁴May be comprised of the same perfluorooxyalkylene units or a mixture of different perfluorooxyalkylene units. When the perfluoroalkoxyalkylene groups are composed of different perfluoroalkyleneoxy units, they are present in an irregular configuration, an alternating configuration, or they are present as blocks. Typical perfluorinated poly (oxyalkylene) groups include:

-[CF₂-CF₂-O]_r-；-[CF(CF₃)-CF₂-O]_s-；-[CF₂CF₂-O]_r-[CF₂O]_t-，-[CF₂CF₂CF₂CF₂-O]_uand

-[CF₂-CF₂-O]_r-[CF(CF₃)-CF₂-O]_s-; wherein each of r, s, t and u is an integer of 1 to 50, preferably 2 to 25. A preferred perfluorooxyalkyl radical corresponding to formula (V) is CF₃-CF₂-CF₂-O-[CF(CF₃)-CF₂O]_s-CF(CF₃)CF₂-, where s is an integer from 2 to 25.

Perfluorooxyalkyl and perfluorooxyalkylene compounds are obtained by oligomerization of hexafluoropropylene oxide to produce terminal carbonyl fluoride groups. The carbonyl fluoride may be converted to an acid, ester or alcohol by reactions known to those skilled in the art. The carbonyl fluoride or acid, ester or alcohol thus obtained may then be further reacted according to known procedures to produce the desired isocyanate-reactive groups.

With respect to formula I, wherein y or z is 1, fluorochemical monofunctional compounds are contemplated, preferably monoalcohols and monoamines. Representative examples of useful fluorochemical monofunctional compounds include the following:

CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂OH、

CF₃(CF₂)₃SO₂N(CH₃)CH(CH₃)CH₂OH、

CF₃(CF₂)₃SO₂N(CH₃)CH₂CH(CH₃)NH₂、

CF₃(CF₂)₃SO₂N(CH₂CH₃)CH₂CH₂SH、

CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂SCH₂CH₂OH、

C₆F₁₃SO₂N(CH₃)(CH₂)₄OH、

CF₃(CF₂)₇SO₂N(H)(CH₂)₃OH、C₃F₇SO₂N(CH₃)CH₂CH₂OH、

CF₃(CF₂)₄SO₂N(CH₃)(CH₂)₄NH₂、C₄F₉SO₂N(CH₃)(CH₂)₁₁OH、

CF₃(CF₂)₅SO₂N(CH₂CH₃)CH₂CH₂OH、

CF₃(CF₂)₅SO₂N(C₂H₅)(CH₂)₆OH、

CF₃(CF₂)₂SO₂N(C₂H₅)(CH₂)₄OH、

CF₃(CF₂)₃SO₂N(C₃H₇)CH₂OCH₂CH₂CH₂OH、

CF₃(CF₂)₄SO₂N(CH₂CH₂CH₃)CH₂CH₂OH、

CF₃(CF₂)₄SO₂N(CH₂CH₂CH₃)CH₂CH₂NHCH₃、

CF₃(CF₂)₃SO₂N(C₄H₉)CH₂CH₂NH₂、

CF₃(CF₂)₃SO₂N(C₄H₉)(CH₂)₄SH、

CF₃(CF₂)₃CH₂CH₂OH、C₄F₉OC₂F₄OCF₂CH₂OCH₂CH₂OH；

n-C₆F₁₃CF(CF₃)CON(H)CH₂CH₂OH；

C₆F₁₃CF(CF₃)CO₂C₂H₄CH(CH₃)OH；

C₃F₇CON(H)CH₂CH₂OH；C₃F₇O(CF(CF₃)CF₂O)_1-36CF(CF₃)CH₂OH; and

C₃F₇O(CF(CF₃)CF₂O)_1-36CF(CF₃)C(O)N(H)CH₂CH₂OH, and the like, and mixtures thereof. If desired, other isocyanate-reactive functional groups may be used in place of those shown.

With respect to formula I, wherein y or z is 2, fluorinated polyols are preferred.

Representative examples of suitable fluorinated polyols include: r_f ¹SO₂N(CH₂CH₂OH)₂Such as N-bis (2-hydroxyethyl) perfluorobutanesulfonamide; r_f ¹OC₆H₄SO₂N(CH₂CH₂OH)₂；R_f ¹SO₂N(R’)CH₂CH(OH)CH₂OH, e.g. C₆F₁₃SO₂N(C₃H₇)CH₂CH(OH)CH₂OH；R_f ¹CH₂CON(CH₂CH₂OH)₂；CF₃CF₂(OCF₂CF₂)₃OCF₂CON(CH₃)CH₂CH(OH)CH₂OH；R_f ¹OCH₂CH(OH)CH₂OH, e.g. C₄F₉OCH₂CH(OH)CH₂OH；R_f ¹CH₂CH₂SC₃H₆OCH₂CH(OH)CH₂OH；R_f ¹CH₂CH₂SC₃H₆CH(CH₂OH)₂；R_f ¹CH₂CH₂SCH₂CH(OH)CH₂OH；R_f ¹CH₂CH₂SCH(CH₂OH)CH₂CH₂OH；R_f ¹CH₂CH₂CH₂SCH₂CH(OH)CH₂OH, e.g. C₅F₁₁(CH₂)₃SCH₂CH(OH)CH₂OH；R_f ¹CH₂CH₂CH₂OCH₂CH(OH)CH₂OH, e.g. C₅F₁₁(CH₂)₃OCH₂CH(OH)CH₂OH；R_f ¹CH₂CH₂CH₂OC₂H₄OCH₂CH(OH)CH₂OH；R_f ¹CH₂CH₂(CH₃)OCH₂CH(OH)CH₂OH；R_f ¹(CH₂)₄SC₃H₆CH(CH₂OH)CH₂OH；R_f ¹(CH₂)₄SCH₂CH(CH₂OH)₂；R_f ¹(CH₂)₄SC₃H₆OCH₂CH(OH)CH₂OH；R_f ¹CH₂CH(C₄H₉)SCH₂CH(OH)CH₂OH；R_f ¹CH₂OCH₂CH(OH)CH₂OH；R_f ¹CH2CH(OH)CH₂SCH₂CH₂OH；R_f ¹CH₂CH(OH)CH₂SCH₂CH₂OH；R_f ¹CH₂CH(OH)CH₂OCH₂CH₂OH；R_f ¹CH₂CH(OH)CH₂OHR_f ¹R”SCH(R”’OH)CH(R”’OH)SR”R_f；(R_f ¹CH₂CH₂SCH₂CH₂SCH₂)₂C(CH₂OH)₂；((CF₃)₂CFO(CF₂)₂(CH₂)₂SCH₂)₂C(CH₂OH)₂；(R_f ¹R”SCH₂)₂C(CH₂OH)₂(ii) a 1, 4-bis (1-hydroxy-1, 1-dihydroperfluoroethoxyethoxy) perfluoro-n-butane (HOCH)₂CF₂OC₂F₄O(CF₂)₄OC₂F₄OCF₂CH₂OH); 1, 4-bis (1-hydroxy-1, 1-dihydroperfluoropropoxy)Alkyl) perfluoro-n-butane (HOCH)₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH); fluorinated oxetane polyols are made by ring-opening polymerization of fluorinated oxetanes, for example Poly-3-Fox^TM(commercially available from Omnova solutions of akron, ohio); polyether polyols are prepared by the ring-opening addition polymerization of an epoxy group substituted with a fluorinated organic group and a compound containing at least two hydroxyl groups, as described in U.S. Pat. No.4,508,916(Newell et al); and perfluoropolyether diols such as Fomblin^TM ZDOL(HOCH₂CF₂O(CF₂O)_8-12(CF₂CF₂O)_8-12CF₂CH₂OH from Ausimont); wherein R is_fIs a perfluoroalkyl group having 1 to 12 carbon atoms, or a perfluorooxyalkyl group having 3 to about 50 carbon atoms, all perfluorocarbon chains present in the perfluorooxyalkyl group having 6 or less carbon atoms, or a mixture thereof; r' is an alkyl group of 1 to 4 carbon atoms; r "is a branched or straight chain alkylene group of 1 to 12 carbon atoms, an alkylenethio-alkylene group of 2 to 12 carbon atoms, an alkylene-oxyalkylene group of 2 to 12 carbon atoms, or an alkyleneiminoalkylene group of 2 to 12 carbon atoms, wherein hydrogen or an alkyl group of 1 to 6 carbon atoms is contained as a third substituent; and R' "is a straight or branched alkylene group of 1 to 12 carbon atoms or formula C_rH_2r(OC_SH_2S)_tWherein r is 1-12, s is 2-6, and t is 1-40.

Preferred fluorinated polyols include N-bis (2-hydroxyethyl) perfluorobutanesulfonamide; fluorinated oxetane polyols are made by ring-opening polymerization of fluorinated oxetanes, for example, Poly-3-Fox^TM(commercially available from Omnova solutions of akron, ohio); polyether polyols are prepared by the ring-opening addition polymerization of epoxy-substituted fluorinated organic groups with compounds containing at least two hydroxyl groups, as described in U.S. Pat. No.4,508,916(Newell et al); perfluoropolyether diols such as Fomblin^TM ZDOL(HOCH₂CF₂O(CF₂O)_8-12(CF₂CF₂O)_8-12CF₂CH₂OH from Ausimont); 1, 4-bis (1-hydroxy-1, 1-dihydroperfluoroethoxyethoxy) perfluoro-n-butane (HOCH)₂CF₂OC₂F₄O(CF₂)₄OC₂F₄OCF₂CH₂OH); and 1, 4-bis (1-hydroxy-1, 1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH)₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH)。

More preferred polyols comprised of at least one fluorine-containing group include N-bis (2-hydroxyethyl) perfluorobutanesulfonamide; 1, 4-bis (1-hydroxy-1, 1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH)₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH) and CF₃CF₂CF₂-O-[CF(CF₃)CF₂O]_n-CF(CF₃) -, where n is an integer of 3 to 25. The perfluorinated polyether group may be derived from an oligomerization reaction of hexafluoropropylene oxide. Such perfluorinated polyether groups are particularly preferred due to their good environmental properties.

Fluorochemical urethanes include, in part, the reaction product of a nucleophilic acryloyl compound having an isocyanate-reactive, nucleophilic functional group and at least one acryloyl group (hereinafter "nucleophilic acryloyl compound"). The acryloyl moiety may be acrylate or acrylamide and the nucleophilic functional group may be amino or hydroxyl. Preferably, the nucleophilic acryloyl compound is a polyacryl compound having a hydroxyl group and at least two acryloyl groups.

Such compounds include those of the following formulae:

wherein

X¹is-O-or-S-, preferably-O-;

X²is-O, -S-or-NR⁴-, preferably-O-, in which R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

R³is a polyvalent alkylene or arylene group, or combinations thereof, said alkylene group optionally containing one or more catenary oxygen atoms; and q is 1 to 5.

Preferably q is greater than 1. The resulting polyacryl group causes the addition of a polysilyl group to the urethane compound. Silyl groups with-NH-C (O) -X¹The molar ratio of the radicals may be greater than 1: 1, or greater than 2: 1. Preferably HX¹Not directly attached to the aromatic ring, for example using phenolic compounds.

Useful nucleophilic acryloyl compounds include, for example, acrylate compounds selected from the group consisting of: (a) monoacryloyl-containing compounds, for example hydroxyethyl acrylate, glycerol monoacrylate, 1, 3-butanediol monoacrylate, 1, 4-butanediol monoacrylate, 1, 6-hexanediol monoacrylate, alkoxylated aliphatic monoacrylates, cyclohexane dimethanol monoacrylate, alkoxylated hexanediol monoacrylate, alkoxylated neopentyl glycol monoacrylate, caprolactone-modified neopentyl glycol hydroxypivalate acrylate, caprolactone-modified neopentyl glycol hydroxypivalate monoacrylate, diethylene glycol monoacrylate, dipropylene glycol monoacrylate, ethoxylated bisphenol A monoacrylate, hydroxypivaldehyde-modified trimethylolpropane monoacrylate, neopentyl glycol monoacrylate, propoxylated neopentyl glycol monoacrylate, tetraethylene glycol monoacrylate, mixtures thereof, and mixtures thereof, Tricyclodecanedimethanol monoacrylate, triethylene glycol monoacrylate, tripropylene glycol monoacrylate; (b) polyacryl-containing compounds such as glycerol diacrylate, ethoxylated triacrylates (e.g., ethoxylated trimethylolpropane diacrylate), pentaerythritol triacrylate, propoxylated diacrylates (e.g., propoxylated (3) glycerol diacrylate, propoxylated (5.5) glycerol diacrylate, propoxylated (3) trimethylolpropane diacrylate, propoxylated (6) trimethylolpropane diacrylate), trimethylolpropane diacrylate, higher functionality (meth) acryloyl-containing compounds such as ditrimethylolpropane tetraacrylate, and dipentaerythritol pentaacrylate.

Such compounds are widely available from suppliers such as sandomar, inc, of iscston, pennsylvania; UCB chemicals, georgia smyrna city; and aldrich chemical company of milwaukee, wisconsin. Additional useful acrylate materials include polyacrylates containing dihydroxyhydantoin moieties, such as described in U.S. Pat. No.4,262,072 (Wendling et al) ().

With respect to exemplary nucleophilic acryloyl compounds, it will be understood that the corresponding acrylamides may be used. In addition, the indicated hydroxyl groups may be substituted by corresponding thiol groups.

Fluorochemical urethanes include, in part, the Michael reaction product of an aminosilane with an acryloyl group. The aminosilane may be reacted with a nucleophilic acryloyl compound to form a michael adduct, which may be subsequently reacted with the polyisocyanate (either before or after the process of acting through the nucleophilic fluorine-containing compound). Preferably, the nucleophilic acryloyl compound is first reacted with the polyisocyanate (again, before or after reaction with the nucleophilic fluorine-containing compound) to form a carbamate compound having a pendant acryloyl group to which the aminosilane is added by a michael reaction.

Preferred aminosilanes may be represented by the general formula:

wherein

R⁵Is H, C₁-C₄Alkyl, or-R⁶-Si(Y_p)(R⁷)_3-p；

R⁶Is a divalent alkylene group, optionally containing one or more catenary oxygen atoms;

y is a hydrolyzable group, and Y is a hydrolyzable group,

R⁷is a monovalent alkyl or aryl radical, and is,

p is 1, 2 or 3, preferably 3.

It is understood that in the presence of water, the Y groups may hydrolyze to-OH groups resulting in reaction with the substrate surface to form siloxane bonds, and that the resulting Si-O-Si bonds in particular are water resistant and may provide enhanced durability of stain removal characteristics imparted by the chemical compositions of the present invention.

With regard to the aminosilanes of formula VII, it should be noted that primary amines are mentioned, where R is⁵Those that are H are capable of reacting with two acryloyl groups via michael addition, which can result in crosslinking of the fluorochemical urethane compounds of formula I. In addition, primary amines can also compete with the michael addition of aminosilanes to acryl groups. For these reasons, R⁵H is not preferred, although 20 mole% of such primary aminosilanes may be used.

Some aminosilanes useful in the practice of the present invention are described in U.S. Pat. No.4,378,250 and include aminoethyl triethoxysilane, beta-aminoethyl trimethoxysilane, beta-aminoethyl triethoxysilane, beta-aminoethyl tributoxysilane, beta-aminoethyl tripropoxysilane, alpha-amino-ethyltrimethoxysilane, alpha-aminoethyl triethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltributoxysilane, gamma-aminopropyltripropoxysilane, beta-aminopropyltrimethoxysilane, beta-aminopropyltriethoxysilane, beta-aminopropyltripropoxysilane, beta-aminopropyltributoxysilane, beta-aminoethyltrimethoxysilane, beta-aminopropyltrimethoxysilane, beta-aminopropyltripropoxysilane, beta-aminopropyltributoxysilane, beta-aminobutyltrimethoxysilane, beta-aminoethyltrimethoxysilane, beta-ethyltrimethoxysilane, beta-aminoethyltrimethoxysilane, beta-aminopropyltriethoxysilane, beta-aminopropyl, Alpha-aminopropyltrimethoxysilane, alpha-aminopropyltriethoxysilane, alpha-aminopropyltributoxysilane, alpha-aminopropyltripropoxysilane,

small amounts (< 20 mole%) of aminosilanes containing nitrogen in the chain may also be used, including those described in us 4,378,250: n- (beta-aminoethyl) -beta-aminoethyl-trimethoxysilane, N- (beta-aminoethyl) -beta-aminoethyl-triethoxysilane, N- (beta-aminoethyl) -beta-aminoethyl-tripropoxysilane, N- (beta-aminoethyl) -alpha-aminoethyl-trimethoxysilane, N- (beta-aminoethyl) -alpha-aminoethyl-triethoxysilane, N- (beta-aminoethyl) -alpha-aminoethyl-tripropoxysilane, N- (beta-aminoethyl) -beta-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltripropoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -beta-aminopropyltriethoxysilane, N- (beta-aminoethyl) -beta-aminopropyltripropoxysilane, N- (gamma-aminoethyl) -beta-aminoethyltrimethoxysilane, N- (gamma-aminoethyl) -beta-aminoethyltriethoxysilane, N- (gamma-aminoethyl) -beta-aminoethyltripropoxysilane, N-methylaminopropyltrimethoxysilane, beta-aminopropylmethyldiethoxysilane, and gamma-diethylenetriaminopropyltriethoxysilane.

The fluorine-containing compound can be prepared by simply mixing a nucleophilic acryloyl compound, a fluorine-containing nucleophilic compound, and a polyisocyanate compound to produce a carbamate of the formula:

wherein

R_fIs a fluorine-containing group including a monovalent perfluoroalkyl group or a perfluorooxyalkyl group, or a divalent perfluoroalkylene group or a perfluorooxyalkylene group,

R¹is the residue of a polyisocyanate, and is,

X¹is-O-or-S-,

X²is-O, -S-or-NR⁴-, wherein R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

R³is a divalent alkylene or arylene group, or combinations thereof, the alkylene group optionally containing one or more catenary oxygen atoms;

x is 1 or 2, and the compound is,

z is 1 or 2, and

q is 1 to 5.

Aminosilane (VII) is then subjected to a Michael addition with an acryloyl group. As will be appreciated by those skilled in the art, the order of mixing or the order of steps is not limiting and can be varied to produce the desired fluorochemical urethane compounds. In a preferred embodiment, the polyisocyanate compound, the fluorine-containing nucleophilic compound (III), is first reacted with some portion of the isocyanate groups, whereby the pendant fluorine-containing groups are thus bonded to the urethane compounds of the isocyanate functional groups. The nucleophilic acryloyl compound is then reacted with some portion of the remaining isocyanate groups, followed by the michael addition of an aminosilane to the pendant acryloyl groups. Where the nucleophilic fluorine-containing compound is an amine, this is usually further functionalized by the nucleophilic acryloyl compound since the amine functionality will compete with the michael addition through the aminosilane.

Typically, the reactive components and solvent are charged to the dry reaction vessel either immediately continuously or as a pre-formed mixture. When a homogeneous mixture or solvent is obtained, optionally with the addition of a catalyst, the reaction mixture is heated at a temperature and for a time sufficient for the reaction to occur. The progress of the reaction can be determined by monitoring the disappearance of the isocyanate peak in the IR.

Using a sufficient amount of a nucleophilic compound R_f ¹-Q(X²H)_z(III) with 5 to 50 mole% of available isocyanate functional groups. Preferably, compounds III are used which react with from 10 to 30 mol% of isocyanate groups. About 50 to 95 mol%, preferably 70 to 90 mol%, of the remaining isocyanate groups are functionalized by the nucleophilic acryloyl compound (VI), followed by the michael addition reaction of the aminosilane (VII), to produce a carbamate compound having a pendant fluorochemical group and a pendant acryloyl group.

Alternatively, aminosilane (VII) and nucleophilic acryloyl compound (VI) may be pre-reacted, followed by reaction of the Michael adduct of formula IX with the remaining isocyanate groups. By IR, the fluorochemical urethane compounds corresponding to formula I are generally substantially free of remaining isocyanate groups.

Depending on the reaction conditions (e.g., reaction temperature and/or polyisocyanate used), a catalyst content of up to about 0.5% by weight of the reaction mixture may be used to effect the condensation reaction with the isocyanate, but typically from about 0.00005 to about 0.5% by weight, preferably from 0.02 to 0.1% by weight, may be used. Typically, if the nucleophilic group is an amine group, a catalyst is not necessary.

Suitable catalysts include, but are not limited to, tertiary amines and tin compounds. Examples of useful tin compounds include tin II and tin IV salts, such as stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di-2-ethyl hexanoate, and dibutyltin oxide. Examples of useful tertiary amine compounds include triethylamine, tributylamine, triethylenediamine, tripropylamine, bis (dimethylaminoethyl) ether, morpholine compounds such as ethyl morpholine and 2, 2' -dimorpholinodiethyl ether, 1, 4-diazabicyclo [2.2.2] octane (DABCO, Aldrich chemical company of Milwaukee, Wis.), ethyl 1, 8-diazabicyclo [5.4.0.] undec-7-ene (DBU, Aldrich chemical company of Milwaukee, Wis.). Tin compounds are preferred. If an acid catalyst is used, it is preferred that it be removed or neutralized from the product after the reaction. It has been found that the presence of the catalyst can adversely affect contact angle performance.

Although no catalyst is required for the michael addition reaction of an aminosilane with an acryloyl group, a suitable catalyst for the michael reaction is a base of its conjugate acid preferably having a pKa between 12 and 14. Most preferably the base used is organic. Examples of such bases are 1, 4-dihydroxypyrimidine, methyldiphenylphosphine, methyl-di-p-tolylphosphine, 2-allyl-N-alkylimidazoline, tetra-tert-tetrabutylammonium hydroxide, DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene) and DBN (1, 5-diazabicyclo [4.3.0] nona-5-ene), potassium methoxide, sodium hydroxide and the like. Preferred catalysts in connection with the present invention are DBU and tetramethylguanidine. The amount of catalyst used in the michael addition reaction is preferably between 0.05 wt% and 2 wt%, more preferably between 0.1 wt% and 1.0 wt%, relative to the solids.

The composition according to the present invention may be coated on a substrate and at least partially cured to provide a coated article. In some embodiments, the polymeric coating may form a protective coating that provides at least one of scratch resistance, smear resistance, stain resistance, adhesive release, low refractive index, water resistance. Coated articles according to the present invention include, for example, ophthalmic lenses, mirrors, windows, adhesive release liners, and anti-smear films.

Suitable substrates include, for example, glass (windows and optical elements such as lenses and mirrors), ceramics (e.g., ceramic tiles), cements, stone, painted surfaces (e.g., automobile covers, boat surfaces), metals (e.g., building studs), paper (e.g., adhesive release liners), cardboard (e.g., food containers), thermosets, thermoplastics (e.g., polycarbonates, acrylics, polyolefins, urethanes, polyesters, polyamides, polyimides, phenolic resins, cellulose diacetate, cellulose triacetate, polystyrene, and styrene-acrylonitrile copolymers), and combinations thereof. The substrate may be a film, a sheet, or it may have some other form. The substrate may comprise a transparent or translucent display element, optionally having a ceramic polymer hardcoat thereon.

In some embodiments, a coating composition is provided that includes a mixture of fluorochemical urethane compounds and a solvent. The coating composition of the present invention comprises a solvent suspension, dispersion or solution of the fluorochemical compound of the present invention. When applied as a coating, the coating composition imparts oil and water repellency, and/or stain release and stain repellency characteristics to any of a wide variety of substrates.

The fluorochemical compound can be dissolved, suspended, or dispersed in a variety of solvents to form a coating composition suitable for coating on a substrate. Generally, the solvent solution may comprise (based on the total weight of the solid components) from about 0.1 to about 50 wt%, or even up to about 90 wt%, of non-volatile solids. The coating composition preferably comprises about 0.1 to about 10 weight percent fluorochemical urethane compounds based on total solids. The amount of fluorochemical urethane compound used in the coating is preferably from about 0.1 to about 5 weight percent of the total solids, most preferably from about 0.2 to about 1 weight percent. Suitable solvents include alcohols, esters, glycols, amides, ketones, hydrocarbons, hydrofluorocarbons, hydrofluoroethers, chlorocarbons, and mixtures thereof.

For ease of manufacture and cost reasons, the compositions of the present invention may be prepared immediately prior to use by diluting a concentrate of one or more compounds of formula I. The concentrate generally comprises a concentrated solution of the fluorochemical urethane compound in an organic solvent. The concentrate should be stable for several weeks, preferably at least 1 month, more preferably at least 3 months. It has been found that the compounds can be readily dissolved in organic solvents at high concentrations.

The coating composition of the present invention optionally comprises a silsesquioxane. The silsesquioxane can be blended with the coating composition or, alternatively, formula IThe coating of the compound of (a) can be coated onto a previously applied silsesquioxane coating. Useful silsesquioxanes include those of the formula R¹⁰ ₂Si(OR¹¹) Diorganooxysilane (or hydrolysate thereof)₂And formula R¹⁰SiO_3/2Of an organosilane (or hydrolysate thereof) in which each R is¹⁰Is an alkyl or aryl group of 1 to 6 carbon atoms, and R¹¹Represents an alkyl group having 1 to 4 carbon atoms. Preferred silsesquioxanes are neutral or anionic silsesquioxanes prior to addition to the composition. Useful silsesquioxanes can be prepared by the techniques described in U.S. Pat. Nos.3,493,424(Mohrlok et al), 4,351,736(Steinberger et al), 5,073,442(Knowlton et al), 4,781,844(Kortmann et al), and 4,781,844. The silsesquioxane may be added in an amount of 90 wt% to 99.9 wt% relative to the total solids.

The silsesquioxane can be prepared by adding silane to a mixture of water, buffer, surfactant, and optionally organic solvent while stirring the mixture under acidic or basic conditions. The amount of silane is preferably added uniformly and slowly so as to obtain a narrow particle size of 200 to 500 angstroms. The exact amount of silane that can be added depends on the substituent R and whether an anionic or cationic surfactant is used. The co-concentrate of the silsesquioxane, in which the units may be present in blocks or irregular distribution, is formed by simultaneous silane hydrolysis. Included among those present are tetraalkoxysilanes and hydrolysates thereof (e.g. of the formula Si (OH))₄Expressed) is less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight, relative to the weight of the silsesquioxane.

The following silanes may be used in the preparation of the silsesquioxanes of the present invention: methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, 2-ethylbutyltriethoxysilane, and 2-ethylbutoxytriethoxysilane.

The composition may be applied to the substrate by conventional techniques such as spraying, knife coating, gravure coating, reverse roll coating, gravure coating, dip coating, bar coating, flood coating, dip coating or spin coating. The composition may be applied to any thickness that provides the desired degree of water repellency, oil repellency, stain repellency, and soil resistance. Typically, the composition is applied to the substrate as a relatively thin layer, resulting in a dried cured layer having a thickness in the range of about 40nm to about 60nm, although thinner and thicker (e.g., having a thickness of up to 100 microns or more) layers may also be used. Next, any optional solvent is typically at least partially removed (e.g., using a forced air oven), and then the composition is at least partially cured to form a durable coating.

A preferred coating method for applying the fluorochemical urethane silane compound of the present invention includes dip coating. The coated substrate may typically be contacted with the treated composition at room temperature (typically about 20 to about 25 ℃). Alternatively, the mixture may be coated onto a substrate that is preheated at a temperature of, for example, 60 to 150 ℃. This is particularly beneficial for industrial production where ceramic patches may be processed immediately after oven baking at the end of the production line, for example. After coating, the treated substrate may be dried and cured at ambient or elevated temperatures, e.g., 40 to 300 ℃, for a sufficient time to dry. The method also requires a grinding step to remove excess material.

The present invention provides a protective coating on a substrate that is relatively durable, more resistant to contaminants, and easier to clean than the substrate surface itself. In one embodiment, the present invention provides a method and composition for preparing a coated article comprising a substrate, preferably a hard substrate, and an anti-smudge coating deposited thereon of greater than a monolayer (typically greater than about 15 angstroms thick). Preferably, the anti-smudge coating of the present invention is at least about 20 angstroms thick, more preferably at least about 30 angstroms thick. Generally, the thickness of the coating is less than 10 microns, preferably less than 5 microns. The coating material is typically present in an amount that does not substantially alter the appearance and optical properties of the article.

Examples of the invention

Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. These examples are for illustrative purposes only and are not intended to limit the scope of the appended claims.

All parts, percentages, ratios, etc. in the examples, as well as the remainder of the specification, are by weight unless otherwise indicated. Solvents and other reagents used were obtained from aldrich chemical company of milwaukee, wisconsin, unless otherwise specified.

Test method

Nuclear Magnetic Resonance (NMR)

¹H and¹⁹the F NMR spectra were run on a warian UNITYplus 400 fourier transform nuclear magnetic resonance spectrometer (obtained from warian nuclear magnetic resonance instruments in palo alto, ca).

IR Spectrum (IR)

The IR spectra were run on a Thermo-Nicolet, Avatar 370 Fourier Infrared transform instrument available from thermoelectrics of Waltham, Massachusetts.

Method for forming coating on polycarbonate plate

A polycarbonate plate (10cm × 10cm) was coated with a coating composition including the fluorochemical urethane composition according to the present invention using a dip coating method. To form the coating, each polycarbonate panel was first immersed in the SHP 401 primer at a rate of 90cm per minute. Once the entire panel was immersed in the primer, the panel was removed from the primer at a rate of 90cm per minute and allowed to dry for 10 minutes at room temperature. The dried sheet was then immersed in a solution of SHC-1200 or a solution of SHC-1200 containing 0.3 wt% fluorochemical urethane silane compound prepared according to the present invention. The panels were immersed in the coating solution at a rate of 90cm per minute, removed at a rate of 19cm per minute, air dried at room temperature for 20 minutes and finally heated in an oven at 130 ℃ for 30 minutes.

Ink repellency test

This test is used to determine the ink repellency of coatings on polycarbonate plates. Coated polycarbonate sheets were prepared as described above. Using Sharpie^TMSmall dot, series 30000 permanent mark (available from seiko-shifu, division of newville group) drawn through the surface of the coated polycarbonate sheet. The appearance and ability to resist black Sharpie labeling of the samples were evaluated.

Durability test for ink repellency

To determine the durability of the ink repellency of the coated polycarbonate plates, a modified oscillatory sand method (ASTM F735-94) was used. The coated polycarbonate plate (i.e., the test sample prepared above) was secured using vinyl tape and rubber tape to a jar having an inner diameter of 87mm (VWR 36318-. The jar was set in a shaker (VWRDS-500E, available from VWR of bristol, connecticut), with the test sample on the bottom side, and the shaker was operated to oscillate at 225rpm for 10 minutes. At the end of 10 minutes, the polycarbonate plate was removed and a line was drawn through its surface in contact with the sand using a Sharpie permanent mark. The normalized (%) length of the 87mm ink line without beading was measured and recorded as percent ink repellency loss. Data reported are the average of three independent tests. Lower numbers indicate good performance.

Taber Haze (Taber Haze) test

The test was performed on the coated polycarbonate described above. The testing procedure is the work order number CET-APRS-STP-0316, version 1.1, published by the national institute for occupational safety and health at 24/10/2005. Numbers less than 4 are desirable.

Steel wool durability test

The abrasion resistance of the coated and cured polycarbonate (prepared as described above) was measured in the cross-web to coating direction by using a mechanical device capable of oscillating a steel wool sheet adhered to a stylus passing through the surface of the film. The stylus was oscillated at a rate of 315 mm/sec (3.5 scans/sec) over a scan width of 90mm width, where "scan" is defined as a single stroke of 90 mm. The stylus has a flat, cylindrical basic geometry with a diameter of 3.2 cm. The stylus is designed to be able to attach an additional weight to increase the force applied through the steel wool perpendicular to the surface of the film. The samples were tested with 25 scans at a 500g load. Steel wool #0000 is Hut product "magic sand-abrasive sheet" from velton, missouri. #0000 had the specified grit equivalence of 600-1200 grit sandpaper. A 3.2cm steel wool disc was die cut from the matte and adhered to a 3.2cm stylus base using a 3M brand Scotch permanent adhesive transfer tape. After steel wool abrasion, the contact angles were measured on the abraded traces and on the area of the plate adjacent to the abraded traces, which was not affected by the steel wool traces (i.e. before steel wool testing). The contact angle measurement was performed using the "method of measuring contact angle" described below. The data recorded represent the average of measurements made on 3 plates. Three drops were placed on each plate and the contact angle was measured on the right and left side of each drop.

Method for measuring contact angle

Coated polycarbonate plaques (prepared as described above) were treated with IPA, which was evaporated prior to being subjected to measurement of water contact angle. Measurements were performed on a video contact angle analyzer (available as product number VCA-2500XE from AST products of belerica, massachusetts) using a directly usable reagent grade hexadecane and deionized water filtered through a filtration system (available from millipore corporation of belerica, massachusetts). The values reported are the average of the measurements made for at least three drops (measured on the right and left side of the drop). For the measurement of static contact angle, the volume of the drop was 5 μ L.

Solvent resistance test

The four chambers were filled with different solvents: ethanol, isopropanol, toluene, and methyl ethyl ketone. Each plate prepared as described above was placed in all four chambers for 60 seconds. Observations such as peeling, cracking, discoloration, and any other changes in the coating were recorded. The plates were then placed in the solvent chamber for an additional 300 seconds. All observations were again recorded.

Material

Hexamethylene diisocyanate (Desmodur) ^TM N100)Available from Bayer Polymers LLC of Pittsburgh, Pa.

HFPO-C(O)N(H)CH ₂ CH ₂ OHPrepared by a similar procedure as described in U.S. patent publication No.2004-0077775 entitled "fluorochemical compositions comprising fluorochemical polymers and treatment of fibrous substrates formed therefrom".

Pentaerythritol triacrylate (PET) ₃ A)Available from Sartomer Company (Sartomer Company) under the trade designation SR444C, iscston, pa.

Poly (methyl methacrylate) primer(SHP ^TM 401)GE silicone available from walford, new york.

Methylsilsesquioxane Solution (SHC) ^TM 1200)Available from GE silicone company, wotford, new york.

N-methylaminopropyltrimethoxysilane (MAPTMS)Available from Union Carbide chemistry and plastics, Inc. of Danbury, Connecticut, U.S. (Union Carbide Chemicals and plastics Co.).

Bis (propyl-3-trimethoxy silane) amineAvailable from Gelest corporation of molysi, pa.

Aminopropyl trimethoxysilane (APTMS)Available from sigma aldrich of milwaukee, wisconsin.

Hydroxyethyl acrylate (HEA)Available from sigma aldrich of milwaukee, wisconsin.

Dibutyltin dilaurate (DBTDL)Available from sigma aldrich of milwaukee, wisconsin.

Polycarbonate plateMinnesota Mold from Vadnais high, Minnesota&Engineering (available under the trade name GE Lexan)^TM101, mantenon, indiana).

Example 1

a)[DESN100/0.15HFPOC(O)N(H)CH ₂ CH ₂ OH/0.90HEA]Of intermediates Preparation of

A200 mL round bottom flask equipped with a stir bar was charged with 12.5g (0.0654 equivalents, 1.0 mole fraction, 191.0 isocyanate equivalents) DESN100, 1.6mg (50 ppm relative to solids) DBTDL, 0.05g BHT, and 32.24g THF to form a mixture. The flask was placed in a 55 ℃ water bath and 12.90g (0.0098 eq, 0.15 mole fraction, 1314 molecular weight) HFPOC (O) N (H) CH₂CH₂OH was added to the mixture over 10 minutes via a pressure-regulated dropping funnel. Two hours after the addition was complete, 6.84g (0.0589 equivalents, 0.85 mole fraction) of hydroxyethyl acrylate was added and the mixture was allowed to react overnight. After overnight reaction, the IR spectrum of the sample was 2265cm^-1There are no peaks corresponding to NCO groups. The product of the reaction was diluted by the addition of 5.48g of THF to adjust its composition to 50% solids.

b) Preparation of perfluoropolyether urethane silanes

5g of the intermediate prepared in a) above (0.004565 moles of acrylate functions) were charged to a 25ml round bottom flask equipped with a magnetic stir bar. The flask was placed in an oil bath and the contents of the flask were placed under a nitrogen atmosphere. 1.56g (0.004565 moles) of bis (trimethoxysilylpropyl) amine was added dropwise to the flask at room temperature. The reaction mixture was stirred at room temperature for 15 minutes and then heated to 55 ℃ for 4 hours. The reaction is completed by¹The disappearance of the acrylate peak in the H NMR spectrum. Prior to coating, the product was stored in amber bottles under nitrogen atmosphere in a refrigerator.

Example 2

a)[DESN100/0.30HFPOC(O)N(H)CH ₂ CH ₂ OH/0.75HEA]Of intermediates Preparation of

A200 mL round bottom flask equipped with a stir bar was charged with 12.5g (0.0654 equivalents, 1.0 mole fraction) of DESN100, 1.6mg DBTDL, 0.05g BHT, and 44.0g THF to form a mixture. The flask was placed in a bath at 55 deg.C and 25.80g (0.0196K)Amount, 0.30 mole fraction, 1314 molecular weight) HFPOC (O) N (H) CH₂CH₂OH was added to the mixture over 10 minutes via a pressure-regulated dropping funnel. Two hours after the addition was complete, 5.70g (0.0491 equivalents, 0.75 mole fraction) of hydroxyethyl acrylate was added and the mixture was allowed to react overnight. After overnight reaction, the IR spectrum of the sample was 2265cm^-1There are no peaks corresponding to NCO groups. The product of the reaction was diluted by adding 11.44g of THF to adjust its composition to 50% solids.

b) Preparation of perfluoropolyether urethane silanes

5g of the intermediate prepared in a) above (0.00278 moles of acrylate functions) were charged to a 25ml round bottom flask equipped with a magnetic stir bar. The flask was placed in an oil bath and the contents of the flask were placed under a nitrogen atmosphere. 0.9493g (0.00278 moles) of bis (trimethoxysilylpropyl) amine was added dropwise to the flask at room temperature. The reaction mixture was stirred at room temperature for 15 minutes and then heated to 55 ℃ for 4 hours. The reaction is completed by¹The disappearance of the acrylate peak in the HNMR spectrum. Prior to coating, the product was stored in amber bottles under nitrogen atmosphere in a refrigerator.

Example 3

a)[DESN100/0.50HFPOC(O)N(H)CH ₂ CH ₂ OH/0.55HEA]Of intermediates Preparation of

A200 mL round bottom flask equipped with a stir bar was charged with 12.5g (0.0654 equivalents, 1.0 mole fraction) of DESN100, 1.6mg DBTDL, 0.05g BHT, and 59.88g THF to form a mixture. The flask was placed in a 55 ℃ bath and 43.0g (0.0327 eq., 0.50 mole fraction, 1314 molecular weight) of HFPOC (O) N (H) CH₂CH₂OH was added to the mixture over 10 minutes via a pressure-regulated dropping funnel. Two hours after the addition was complete, 4.18g (0.0360 equivalents, 0.55 mole fraction) were added) Hydroxyethyl acrylate and the mixture was allowed to react overnight. After overnight reaction, the IR spectrum of the sample was 2265cm^-1There are no peaks corresponding to NCO groups. The product of the reaction was adjusted to 50% solids by adding 29.62g of THF.

b) Preparation of perfluoropolyether urethane silanes

5g of the intermediate prepared in a) above (0.0015 moles of acrylate functions) are charged to a 25ml round bottom flask equipped with a magnetic stir bar. The flask was placed in an oil bath and the contents of the flask were placed under a nitrogen atmosphere. 0.5138g (0.0015 moles) of bis (trimethoxysilylpropyl) amine was added dropwise to the flask at room temperature. The reaction mixture was stirred at room temperature for 15 minutes and then heated to 55 ℃ for 4 hours. The reaction is completed by¹The disappearance of the acrylate peak in the H NMR spectrum. Prior to coating, the product was stored in amber bottles under nitrogen atmosphere in a refrigerator.

Example 4

a)[DESN100/ 75％ HEA/ 15％ PET ₃ A/ 15％ HFPOC(O)NHCH ₂ CH ₂ OH]Preparation of intermediates

A200 mL round bottom flask equipped with a stir bar was charged with 12.5g (0.0654 equivalents, 1.0 mole fraction) of DESN100, 1.6mg DBTDL, 0.05g BHT, and 35.24g THF to form a mixture. The flask was placed in a bath at 55 deg.C and 12.9g (0.0098 equivalents, 0.15 mole fraction, 1314 molecular weight) of HFPOC (O) N (H) CH₂CH₂OH was added to the mixture over 10 minutes via a pressure-regulated dropping funnel. Two hours after the addition was complete, 4.13g (0.0098 eq, 0.15 mole fraction) of PET was added₃A is added to the mixture. Two hours after the completion of the addition, 5.70g (0.0491 equivalents, 0.75 mole fraction) of hydroxyethyl acrylate was added,the mixture was allowed to react overnight. After overnight reaction, the IR spectrum of the sample was 2265cm^-1There are no peaks corresponding to NCO groups. The product of the reaction was adjusted to 50% solids by dilution with 5.48g of THF.

b) Preparation of perfluoropolyether urethanes

35.24g of intermediate (0.046) prepared in a) above are added^*Molar acrylate functionality) was charged to a 100ml round bottom flask equipped with a magnetic stir bar. The flask was placed in an oil bath and the contents of the flask were placed under a nitrogen atmosphere. 15.77g (1.417 equivalents, 0.046 mole fraction) of bis (trimethoxysilylpropyl) amine was added dropwise to the flask at room temperature. The reaction mixture was stirred at room temperature for 15 minutes and then heated to 55 ℃ for 4 hours. The reaction is completed by¹Disappearance of acrylate peak in H NMR spectrum. Prior to coating, the product was stored in amber bottles under nitrogen atmosphere in a refrigerator.

^*The number of equivalents of bis (trimethoxysilylpropyl) amine used is determined by: it was first assumed that 420.94OH equivalent of PET was used₃A was 70% pentaerythritol triacrylate (298/421.4) and 30% pentaerythritol tetraacrylate. Secondly, the number of acrylate moieties present per mole OH equivalent is determined by calculation from the following equation: [ total number of all components (number of acrylate moieties present in the component) (hydroxyl equivalent of total material) (component parts of total material) ]]Molecular weight of component (c). For example, the value of pentaerythritol triacrylate in the equation is: [ (3) × (420.94) × (0.7)/(298)]+[(4)×(420.94)×(0.3)/352]4.40. Thus, from the PET prepared in 5a)₃The number of equivalents of acrylate for a and HEA is (0.0098 × 4.40) + (0.0491) ═ 0.0922. Since half of the solution was used for preparation of 5b), the number of moles of acrylate in the reaction was 0.046. Similar calculations were made for examples 6, 7 and 8.

Example 5

Preparation of perfluoropolyether urethane silanes

35.24g of the intermediate (0.046 moles of acrylate functions) prepared as in example 4a) above are charged to a 100ml round bottom flask equipped with a magnetic stir bar. The flask was placed in an oil bath and the contents of the flask were placed under a nitrogen atmosphere. 8.92g (0.046 equivalent)^*1.417 parts) of MAPTMS was added dropwise to the flask at room temperature. The reaction mixture was stirred at room temperature for 15 minutes and then heated to 55 ℃ for 4 hours. The reaction is completed by¹The disappearance of the acrylate peak in the HNMR spectrum. Prior to coating, the product was stored in amber bottles under nitrogen atmosphere in a refrigerator.

Example 6

a)[DESN100/ 60％ HEA/ 30％ PET ₃ A/ 15％ HFPOC(O)NHCH ₂ CH ₂ OH]Preparation of intermediates

A200 mL round bottom flask equipped with a stir bar was charged with 12.5g (0.0654 equivalents, 1.0 mole fraction) of DESN100, 1.6mg DBTDL, 0.05g BHT, and 35.24g THF to form a mixture. The flask was placed in a bath at 55 deg.C and 12.9g (0.0098 equivalents, 0.15 mole fraction, 1314 molecular weight) of HFPOC (O) N (H) CH₂CH₂OH was added to the mixture over 10 minutes via a pressure-regulated dropping funnel. Two hours after the addition was complete, 8.26(0.0196 eq., 0.30 mole fraction) of PET was added₃A is added to the mixture. Two hours after the addition was complete, 4.56g (0.0393 eq, 0.6 mole fraction) of hydroxyethyl acrylate was added and the mixture was allowed to react overnight. After overnight reaction, the IR spectrum of the sample was 2265cm^-1There are no peaks corresponding to NCO groups. The product of the reaction was diluted by the addition of 5.48g of THF to adjust its composition to 50% solids.

b) PerfluoropolyethersPreparation of urethane silanes

38.23g of the intermediate prepared in a) above (0.063 moles of acrylate functions) are charged to a 100ml round bottom flask equipped with a magnetic stir bar. The flask was placed in an oil bath and the contents of the flask were placed under a nitrogen atmosphere. 21.49g (0.063 equivalents, 1.927 mole parts) of bis (trimethoxysilylpropyl) amine were added dropwise to the flask at room temperature. The reaction mixture was stirred at room temperature for 15 minutes and then heated to 55 ℃ for 4 hours. The reaction is completed by¹The disappearance of the acrylate peak in the H NMR spectrum. Prior to coating, the product was stored in amber bottles under nitrogen atmosphere in a refrigerator.

Example 7

Preparation of perfluoropolyether urethane silanes

38.23g of the intermediate prepared in the above example 6a) (0.063 moles of acrylate functions) are charged to a 100ml round bottom flask equipped with a magnetic stir bar. The flask was placed in an oil bath and the contents of the flask were placed under a nitrogen atmosphere. 12.16g (0.63 eq, 1.927 mole fraction) of MAPTMS was added dropwise to the flask at room temperature. The reaction mixture was stirred at room temperature for 15 minutes and then heated to 55 ℃ for 4 hours. The reaction is completed by¹The disappearance of the acrylate peak in the H spectrum. Prior to coating, the product was stored in amber bottles under nitrogen atmosphere in a refrigerator.

The materials of examples 1-7 were used to prepare coatings on polycarbonate sheets according to the "method of forming coatings on polycarbonate sheets" described above. The properties of the resulting coatings were then evaluated using the taber haze change, ink repellency test, ink repellency durability test, steel wool test, and solvent test as described above.

Table 1 below summarizes the results of taber haze change, ink repellency test, ink repellency durability test for coatings made using SHC-1200 and the materials of examples 1-7 without the addition of the fluorochemical urethane silane compound.

TABLE 1

Examples of the invention	Taber haze test	Ink repellency test	Ink repellency durability%
				SHC-1200 control	3.57	4	100
1	3.48	1	7
				2	3.05	2	70
3	3.47	1	97
				4	3.06	1	94
5	2.49	1	94
				6	2.97	1	100
7	3.12	1	100

Table 2 below summarizes the results of the steel wool test for coatings made using SHC-1200 and the materials of examples 1-7 without the addition of the fluorochemical urethane silane compound.

TABLE 2

Table 3 below summarizes the results of solvent testing for coatings made using SHC-1200 and the materials of examples 1-3 without the addition of a fluorochemical urethane silane compound.

TABLE 3

Examples of the invention	Solvent(s)	After 60 seconds	After 300 seconds
				SHC-1200 control	Ethanol	Has no influence on	Has no influence on
SHC-1200 control	Isopropanol (I-propanol)	Has no influence on	Has no influence on
				SHC-1200 control	Toluene	Has no influence on	Has no influence on
SHC-1200 control	MEK	Has no influence on	Small amount of micro-fracture at the edge
				1	Ethanol	Has no influence on	Has no influence on
1	Isopropanol (I-propanol)	Has no influence on	Has no influence on
				1	Toluene	Has no influence on	Small amount of micro-fracture
1	MEK	White spots and elongated fractures	At the edges, there were cracks and some white spots, peeling
				2	Ethanol	Has no influence on	Has no influence on
2	Isopropanol (I-propanol)	Has no influence on	Has no influence on
				2	Toluene	Has no influence on	Small amount of micro-fracture
2	MEK	Has no influence on	Elongated breaks throughout the coating
				3	Ethanol	Has no influence on	Has no influence on
3	Isopropanol (I-propanol)	Has no influence on	Has no influence on
				3	Toluene	Has no influence on	Small amount of micro-fracture
3	MEK	Has no influence on	Small amount of micro-fracture, peeling at the edge

Claims (9)

1. A compound represented by the formula:

wherein

R_fIs a fluorine-containing group, and is,

R¹is the residue of a polyisocyanate, and is,

R²represented by the following formula:

wherein

X¹is-O-or-S-,

X²is-O, -S-or-NR⁴-, wherein R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

R³is a polyvalent alkylene or arylene group, or combinations thereof, said alkylene group optionally containing one or more catenary oxygen atoms;

R⁵is C₁-C₄Alkyl, or-R⁶-Si(Y_p)(R⁷)_3-p；

R⁶Is a divalent alkylene group, optionally containing one or more catenary oxygen atoms;

y is a hydrolyzable group, and Y is a hydrolyzable group,

R⁷is a monovalent alkyl or aryl radical, and is,

p is 1, 2 or 3, and

q is a number of the radicals from 1 to 5,

x and y are each independently at least 1, and z is 1 or 2.

2. The compound of claim 1, wherein R_fIncluding fluorine-containing groups selected from monovalent perfluoroalkyl and perfluorooxyalkyl groups, and divalent perfluoroalkylene and perfluorooxyalkylene groups.

3. The compound of claim 1, wherein R_fRepresented by the following formula:

wherein

R_f ¹Is a monovalent perfluoroalkyl or perfluorooxyalkyl group, or a divalent perfluoroalkylene or perfluorooxyalkylene group,

q is a covalent bond, or a divalent alkylene group optionally containing one or more catenary oxygen atoms,

X²is-O-, -NR⁴-or-S-, wherein R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

y is 1 or 2,

z is 1 or 2.

4. A compound according to claim 3, wherein R_f ¹Is a monovalent perfluorooxyalkyl group, or a divalent perfluorooxyalkylene group comprising one or more perfluorinated repeating units selected from the group consisting of:

-(C_nF_2nO)-、-(CF(Z)O)-、-(CF(Z)C_nF_2nO)-、-(C_nF_2nCF(Z)O)-、-(CF₂CF (Z) O) -, and combinations thereof, wherein n is 1 to 4 and Z is perfluoroalkyl, perfluoroalkoxy, or perfluorooxyalkyl.

5. A compound according to claim 3, wherein R_f ¹Including groups represented by the following formulas:

W-R_f ³-O-R_f ⁴-(R_f ⁵)_q-

wherein

W is fluorine of a monovalent perfluorooxyalkyl group, or the opening ("-") of a divalent perfluorooxyalkylene group;

R_f ³represents a perfluoroalkylene group, and is represented by,

R_f ⁴represents a perfluorooxyalkylene group consisting of a perfluorooxyalkyl group having 1, 2, 3, or 4 carbon atoms or a mixture of such perfluorooxyalkyl groups,

R_f ⁵represents a perfluoroalkylene group, and

q is 0 or 1.

6. The method of claim 2A compound, wherein the perfluorooxyalkylene group is selected from one or more of the group consisting of: - [ CF₂-CF₂-O]_r-；-[CF(CF₃)-CF₂-O]_s-；-[CF₂CF₂-O]_r-[CF₂O]_t-；-[CF₂CF₂CF₂CF₂-O]_u-and- [ CF₂-CF₂-O]_r-[CF(CF₃)-CF₂-O]_s-; wherein each of r, s, t and u is an integer from 1 to 50.

7. The compound of claim 1, wherein Y is halogen, C₁-C₄Alkoxy, or C₁-C₄And (4) acyloxy.

8. The compound of claim 1, wherein a silane group represented by the formula with-NH-c (o) -X¹-the molar ratio of the radicals is greater than 1: 1,

wherein,

R⁵is H, C₁-C₄Alkyl, or-R⁶-Si(Y_p)(R⁷)_3-p；

R⁶Is a divalent alkylene group, optionally containing one or more catenary oxygen atoms;

y is a hydrolyzable group, and Y is a hydrolyzable group,

R⁷is a monovalent alkyl or aryl radical, and is,

p is 1, 2 or 3.

9. The compound of claim 1 derived from a nucleophilic acryloyl compound represented by the formula

Wherein

X¹is-O-or-S-,

X²is-O, -S-or-NR⁴-, wherein R⁴Is H or C₁-C₄An alkyl group, a carboxyl group,

R³is a divalent alkylene or arylene group, or combinations thereof, the alkylene group optionally containing one or more catenary oxygen atoms; and q is 1 to 5, the aminosilane is represented by the following formula:

wherein

R⁵Is H, C₁-C₄Alkyl, or-R⁶-Si(Y_p)(R⁷)_3-p；

R⁶Is a divalent alkylene group, optionally containing one or more catenary oxygen atoms;

y is a hydrolyzable group, and Y is a hydrolyzable group,

R⁷is a monovalent alkyl or aryl radical, and is,

p is 1, 2 or 3.